Benzoylpyrazole compounds, intermediate preparing therefor and herbicides

ABSTRACT

A compound represented by the general formula [I] ##STR1## (wherein R 1  is a C 1  -C 6  alkyl group; R 2  is a C 1  -C 6  alkylsulfonyl group and the like; R 3  and R 4  are each independently hydrogen or a C 1  -C.sub. 6 alkyl group; R 5  is hydrogen or a benzyl group or the like; R 7 , R 8 , R 9  and R 10  are each independently hydrogen or a C 1  -C 6  alkyl group.) or a herbicide containing a salt thereof, intermediate preparing therefor, and the said compound.

This application is a 371 of PCT/JP98/04898 Oct. 29, 1998.

TECHNICAL FIELD

The present invention relates to a novel pyrazole compound substitutedwith a benzoyl group at the 4 position of the pyrazole ring and aherbicide.

BACKGROUND ART

For culturing agrohorticultural crops, many herbicides have been used tocontrol weeds, which required great labor. Herbicides applied, however,have caused chemical injuries on crops, or remained in or polluted theenvironment. It is therefore wanted to develop chemicals firmlyeffective at a smaller dosage thereof and applicable safely. Asherbicides having a pyrazole skeleton substituted by a benzoyl group atthe 4 position of the pyrazole ring, Tokkaihei(Japanese Patent Laid-OpenHei) No. 2-173 has disclosed compounds represented by General formula[A] ##STR2##

WO93/18031 Gazette has disclosed compounds represented by formula [B]##STR3##

WO96/26206 Gazette has disclosed compounds represented by formula [C].##STR4##

It is an object of this invention to provide a herbicide that can beadvantageously synthesized on an industrial scale, is firmly effectiveat a lower dosage, and selectively work on weeds without damaging crops.

DISCLOSURE OF THE INVENTION

That is to say, the present invention is directed to a compoundrepresented by General formula [I] ##STR5## [wherein R¹ is a C₁ -C₆alkyl group; R² is a C₁ -C₆ alkylthio group or a C₁ -C₆ alkylsulfonylgroup; R³ and R⁴ are each independently hydrogen or a C₁ -C₆ alkylgroup; R⁵ is hydrogen or a group selected from the group represented bythe following formula ##STR6## (where R⁶ is halogen, a C₁ -C₆ alkylgroup or a C₁ -C₆ alkoxy group; and n is 0, 1, 2, 3, 4 or 5); R⁷, R⁸, R⁹and R¹⁰ are each independently hydrogen or a C₁ -C₆ alkyl group; and (R⁷or R⁸) and (R⁹ or R¹⁰) may form a single bond], or a salt thereof, and aherbicide containing one or more of the said compounds as activeingredients.

In General formula [I] illustrated above, R¹ is a C₁ -C₆ alkyl group,such as methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl.R² is a C₁ -C₆ alkylthio group, such as methylthio, ethylthio,propylthio and isopropylthio or a C₁ -C₆ alkylsulfonyl group, such asmethylsulfonyl, ethylsulfonyl, propylsulfonyl and isopropylsulfonyl.

R³ and R⁴ are each independently hydrogen or a C₁ -C₆ alkyl group, suchas methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl.

R⁵ is hydrogen or the group represented by the above formula. Examplesinclude a phenylsulfonyl group which may have substituent R⁶, a benzylgroup which may have substituent R⁶, and a phenacyl group which may havesubstituent R⁶.

Preferred examples include phenylsulfonyl, tosyl,2,4,6-trimethylphenylsulfonyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl,4-methoxybenzyl, phenacyl, 4-methylphenacyl, and 3,5-dichlorophenacyl.

R⁶ is hydrogen, halogen such as fluorine, chlorine and bromine; a C₁ -C₆alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, s-butyland t-butyl; or a C₁ -C₆ alkoxy group such as methoxy, ethoxy, propoxy,isopropoxy, butoxy and t-butoxy.

R⁷, R⁸, R⁹ and R¹⁰ are each independently hydrogen or a C₁ -C₆ alkylgroup, such as methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl andt-butyl. (R⁷ or R⁸) and (R⁹ or R¹¹) may form a single bond.

Further, the present invention provides a benzoic acid or a benzoic acidester which are raw materials of the said compounds represented by theabove general formula [I]; a general formula (1) ##STR7## (wherein R¹,R², R⁷ to R¹⁰ are as defined above, and R is hydrogen or a C₁ -C₆ alkylgroup.).

R¹, R², R⁷ to R¹⁰ are as defined above in a general formula (1).

R is hydrogen or a straight chain or branching C₁ -C₆ alkyl group suchas methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,pentyl, hexyl or the like.

BEST MODE OF EMBODYING THE INVENTION

The compounds of this invention can be prepared according to thefollowing reaction scheme: ##STR8## (wherein R¹ to R⁵ and R⁷ to R¹¹ areas defined above. Q is halogen, an alkylcarbonyloxy group, analkoxycarbonyloxy group or a benzoyloxy group, and L is halogen.)

In the process illustrated above, compounds of formulas [VIIa] and[VIIb] can be prepared by reacting one mole of each of compounds offormulas [V] and [VIa] (Q is as defined above), or using an excessiveamount of one of them to react with the other, in the presence of onemole or an excessive amount of a base.

Examples of bases used for this reaction include alkali metal hydroxidessuch as KOH and NaOH, alkali metal carbonates such as sodium carbonateand potassium carbonate, hydroxides of alkaline earth metals such ascalcium hydroxide and magnesium hydroxide, carbonates of alkaline earthmetals such as calcium carbonate, tri(C₁ -C₆ alkyl) amines such astriethylamine and diisopropylethylamine, organic bases such as pyridine,and sodium phosphate.

Examples of solvents used for the reaction include water,dichloromethane, chloroform toluene, ethyl acetate, dimethylformamide(DMF), tetrahydrofuran (THF), dimethoxy ethane (DME) and acetonitrile.

The reaction mixture for the reaction described above is stirred at 0°C.˜50° C. until the reaction is completed. In addition, the reaction canbe carried out in a two-phase system, using a phase-transfer catalystsuch as a quaternary ammonium salt.

Furthermore, the compounds of formulas [VIIa] and [VIIb] may also beprepared by reacting compounds of formulas [V] and [VIb] in the presenceof a dehydrocondensing agent such as dicyclohexylcarboimide (DCC).

Solvents used for this reaction include dichloromethane, chloroform,toluene, ethyl acetate, DMF, THE, DME, acetonitrile and t-pentylalcohol.

The reaction mixture is stirred at -10° C.˜50° C. until the reaction iscompleted. The reaction mixture is treated by a usual process.

The compounds of formulas [VIIa] and [VIIb] are used as a mixture in thefollowing rearrangement reaction.

The rearrangement reaction is carried out in the presence of a cyanocompound and a mild base: one mole of the compounds of formulas [VIIa]and [VIIb] is reacted with 1 to 4 moles, preferably 1 to 2 moles, of abase and 0.01 mole to 1.0 mole, preferably 0.05 mole to 0.2 mole, of acyano compound to give a compound represented by [Ia].

Examples of bases used for the said reaction include alkali metalhydroxides such as KOH and NaOH, alkali metal carbonates such as sodiumcarbonate and potassium carbonate, hydroxides of alkaline earth metalssuch as calcium hydroxide and magnesium hydroxide, carbonates ofalkaline earth metals such as calcium carbonate, tri(C₁ -C₆ alkyl)amines such as triethylamine and diisopropylethylamine, organic basessuch as pyridine, and sodium phosphate.

Examples of cyano compounds are potassium cyanide, sodium cyanide,acetone cyanohydrin, hydrogen cyanide and polymers containing potassiumcyanide. The reaction is completed in a shorter period of time if asmall amount of a phase transfer catalyst, such as crown ether, isadded.

The reaction is carried out at a temperature lower than 80° C.,preferably in the temperature range from room temperature to 40° C.Examples of solvents used for the reaction include 1,2-dichloroethane,toluene, acetonitrile, dichloromethane, chloroform, ethyl acetate, DMF,methyl isobutyl ketone, THF and DME.

The rearrangement reaction may be carried out in an inert solvent in thepresence of a base such as potassium carbonate, sodium carbonate,triethylamine or pyridine. An amount of a base used in the reaction is0.5˜2.0 moles to that of the compounds of formulas [VIIa] and [VIIb].Examples of solvents include THF, dioxane, t-pentyl alcohol and t-butylalcohol. Reaction temperature is preferably from room temperature to theboiling point of a solvent used.

Furthermore, the compound of formula [Ia] can also be prepared from thecompounds of formulas [V] and [VIb] with the use of a base together witha dehydrocondensing agent, such as DCC, without isolating the compoundsof formulas [VIIa] and [VIIb]. Examples of bases used for this reactionare potassium carbonate, sodium carbonate, triethylamine and pyridine.An amount of a base used is preferably 0.5-2.0 moles to that of thecompound of formula [V]. Examples of solvents include THF, dioxane,t-pentyl alcohol and t-butyl alcohol. Reaction temperature is preferablyfrom room temperature to the boiling point of a solvent used.

The compound of formula [I] may be prepared by reacting a compound offormula [Ia] with a compound represented by R⁵ L (R⁵ and L are asdefined above) in the presence of a base. Examples of bases used forthis reaction include alkali metal hydroxides such as KOH and NaOH,alkali metal carbonates such as potassium carbonate and sodiumcarbonate, hydroxides of alkaline earth metals such as calciumhydroxide, carbonates of alkaline earth metals such as calciumcarbonate, tri(C₁ -C₆ alkyl)amines such as triethylamine anddiisopropylethylamine, organic bases such as pyridine, and sodiumphosphate.

Examples of solvents for the reaction include dichloromethane,chloroform, toluene, ethyl acetate, DMF, THF, DME and acetonitrile.

The reaction is carried out in a temperature range from 0° C. to theboiling point of a solvent used until the reaction is completed. Thecompound of formula [I] can also be prepared by a reaction in atwo-phase system of water and a water-insoluble solvent among theabove-mentioned solvents, with the use of a phase-transfer catalyst suchas a quaternary ammonium salt.

5-Hydroxypyrazole compounds represented by General formula [V] may beprepared according to the following processes which have been disclosed,for example, in Tokkaisho(Japanese Patent Laid-Open Sho) No. 62-234069or Tokkaihei(Japanese Patent Laid-Open Hei) No. 3-44375. ##STR9##

A compound represented by General formula (1), an important intermediatefor preparing the compounds of this invention, may be prepared accordingto the following reaction scheme: ##STR10## (wherein R¹, R², R⁷, R⁸, R⁹and R¹⁰ are as defined above and R¹³ is a lower alkyl group.)

A dihydroisoxazole compound represented by General formula (1) may beprepared in a way that an aldoxime compound of formula (2) is reactedwith a halogenating agent such as chlorine, bromine, N-chlorosuccinimide(NCS) or N-bromosuccinimide (NBS), in a solvent including a hydrocarbonsuch as benzene or toluene, an ether such as THF or dioxane, a nitrilesuch as acetonitrile, or DMF, at temperature between -10 and 50° C.,followed by a reaction with a base including an organic base such astriethylamine or a carbonate such as sodium hydrogen carbonate orpotassium carbonate, to give a nitrile oxide compound of formula (3).The obtained nitrile oxide is then reacted with a compound representedby General formula (4) (R⁷, R⁸, R⁹ and R¹⁰ are as defined above, andpreferably hydrogen or methyl), at the atmospheric pressure or underpressure using a pressurizing vessel such as an autoclave, in thepresence of the compound of formula (4) at temperature from -10° C. to150° C. The said nitrile oxide compound of formula (3) can be preparedby reacting an aldoxime compound of formula (2) with a hypohalogen acidsalt such as sodium hypochlorite. ##STR11## (wherein R¹, R², R¹³ are asdefined above, and R¹¹ and R¹² correspond to the above-mentioned R⁷, R⁸,R⁹ or R¹⁰.)

An isoxazole compound represented by General formula (7) may be preparedin a way that the aldoxime compound of formula (2) is reacted with ahalogenating agent such as chlorine, bromine, N-chlorosuccinimide (NCS)or N-bromosuccinimide (NBS), in a solvent including a hydrocarbon suchas benzene or toluene, a halogenated hydrocarbon such as dichloromethaneor chloroform an ether such as THF or dioxane, a nitrile such asacetonitrile, or DMF, at temperature between -10 and 50° C., followed bya reaction with a base including an organic base such as triethylamineor a carbonate such as sodium carbonate or potassium carbonate, to givea nitrile oxide compound of formula (3). The obtained nitrile oxide isthen reacted with a substituted vinyl acetate of formula (8) orsubstituted acetylene of formula (9) in a temperature range from -10° C.to the boiling point of a solvent used.

The isoxazole compound of formula (7) may also be prepared by reactingthe said aldoxime compound of formula (2) with a halogenating agent togive a halogenated compound. The obtained halogenated compound is thenreacted with a base mentioned above, in the presence of the substitutedvinyl acetate of formula (8) or substituted acetylene of formula (9).##STR12## (wherein R¹, R⁷, R⁸, R⁹, R¹⁰ and R¹³ are as defined above andR' is a C₁ -C₆ alkyl group.)

Benzoic acid compounds represented by formula (1-1) may be produced byreacting a 4-Cl compound represented by formula (1-2) with a thiolrepresented by R'SH in the presence of a base to give a 4-SR' compoundrepresented by formula (1-3), followed by the oxidation of the 4-SR'compound.

Examples of bases used for this reaction are alkali metal hydroxidessuch as sodium hydroxide and potassium hydroxide, metal alkoxides suchas sodium methoxide and sodium ethoxide, carbonates such as sodiumcarbonate and potassium carbonate, hydrides such as sodium hydride, andorganic bases such as trieythylamine, diisopropylethylamine,1,8-diazabicyclo[5.4.0]unde-7-cene (DBU) and pyridine. Examples ofsolvents used for the reaction are alcohols such as methanol andethanol, ethers such as THF and DME, amides such as DMF anddimethylacetamide, hydrocarbons such as benzene, toluene and xylene,dimethylsulfoxide (DMSO), and acetonitrile.

The following oxidation reaction is carried out, using an oxidizingagent including a peroxy acid such as hydrogen peroxide, peracetic acid,perbenzoic acid and m-chloroperbenzoic acid, or a hypochlorite such assodium hypochlorite or potassium hypochlorite, in an inert solventincluding water, an organic acid such as acetic acid or a halogenatedhydrocarbon such as dichloromethane, chloroform or carbon tetrachloride.The reaction proceeds smoothly in a temperature range from roomtemperature to the boiling point of a solvent used.

If a compound of formula [I] contains a free hydroxyl group, a saltthereof, particularly an agrohorticulturally acceptable salt, can bederived from the said compound. Examples of agrohorticulturallyacceptable salts are salts of sodium, potassium calcium and ammonium.

Examples of ammonium salts are salts with ions of formula: N⁺ RaRbRcRd(where Ra, Rb, Rc and Rd are each independently hydrogen or, as the casemay be, a C₁ -C₁₀ alkyl substituted with such a group as hydroxy). Incase any of Ra, Rb, Rc and Rd is a substituted alkyl, as the case maybe, it preferably has 1 to 4 carbons.

These derivatives can be prepared by usual processes.

The compound of formula [Ia] of this invention may exist in the form oftautomers as many as shown in the following. These tautomers are allwithin the scope of the present invention. ##STR13## (wherein R¹, R²,R³, R⁴, R⁷, R⁸, R⁹ an R¹⁰ are as defined above.)

The compounds of this invention and various intermediates are obtainedby usual post-treatment after reactions are completed.

The structure of the compounds of the present invention and variousintermediates were determined by using IR, NMR, MS and other availablemeans.

Herbicide

The compounds of the present invention have high herbicidal activity ineither soil or foliage treatment under the conditions of upland cropfarming. They are effective on various upland weeds such as crabgrass,cyperaceous weeds, velvetleaf and pigweed. Compounds that work on weedsselectively without damaging crops, such as corn, wheat, soybean andcotton, are also included in the compounds of the present invention.

The compounds of this invention also include those having activity tocontrol plant growth, such as growth retarding, of useful plants such asagricultural crops, ornamental foliage plants and fruit trees.

The compounds of this invention have excellent herbicidal action onvarious lowland weeds such as barnyard grass, Cyperus difformis,Sagittaria trifolia and Scirpus juncoides. Compounds that work on weedsselectively without damaging rice plants are also included in thecompounds of the present invention.

Moreover, the compounds of this invention may be applied to controlweeds in such places as orchards, lawns, railway passages and vacantlands.

The compounds of the present invention include those having actions tocontrol plant growth, and bactericidal, insecticidal and acaricidalactivities.

The herbicidal composition according to the present invention containsone or more compounds of the present invention as active ingredients.When actually applied, the compound of the present invention can be usedin a pure form without adding any other components. The compounds of thepresent invention can be used in a form of formulation usually employedfor agricultural chemicals, such as wettable powder, granules, powder,emulsifiable concentrates, water soluble chemicals, suspensions andfloables, when they are used as agricultural chemicals. When anagricultural chemical is to form a solid formation, examples ofadditives and carriers include vegetable powder such as soybean powderand wheat powder, fine mineral powder such as diatomaceous earth,apatite, gypsum, talc, bentonite, pyrophylite and clay, and organic andinorganic compounds such as sodium benzoate, urea and Glauber's salt. Inthe case of forming a liquid formulation, petroleum fractions such askerosine, xylene and solvent naphtha, cyclohexane, cyclohexanone, DMF,DMSO, alcohol, acetone, trichloroethylene, methyl isobutyl ketone,mineral oils, vegetable oils and water may be used as a solvent. Inorder to make these formulations uniform and stable, surface activeagents may be added, if required. Any surface active agent may be usedwithout particular restrictions. Examples of surfactants includenon-ionic surface active agents such as polyoxyethylene addedalkylphenyl ethers, polyoxyethylene added alkyl ethers, polyoxyethyleneadded higher fatty acid esters, polyoxyethylene added sorbitan higherfatty acid esters and polyoxyethylene added tristyrylphenyl ethers,sulfates of polyoxyethylene added alkylphenyl ethers, alkylbenzenesulfonates, higher alcohol sulfates, alkyl sulfates, alkylnaphthalenesulfonates, polycarboxylic acid salts, lignin sulfonates, condensationproducts of alkylnaphthalene sulfonates with formaldehyde, andcopolymers of isobutylene and maleic anhydride.

The concentration of an active ingredient in the herbicide of thepresent invention varies depending on a formulation form describedabove. For example, an active ingredient is 5˜90% by weight (hereinafter abbreviated simply as %), preferably 10˜85%, in wettable powder;3˜70%, preferably 5˜60%, in an emulsifiable concentrate; and 0.01˜50%,preferably 0.05˜40%, in a granule.

The wettable powder or emulsifiable concentrate, thus obtained, isdiluted with water to a prescribed concentration in order to use as asuspension or an emulsion. Granules are used as they are. Thesuspension, emulsion or granules may be applied by spraying or admixingbefore or after weeds germinate. When a herbicide of this invention isactually applied, an appropriate amount of the active ingredient is 0.1g or more per hectare.

Furthermore, a herbicide of the present invention may be used as amixture with known agents such as fungicides, insecticides, acaricides,other herbicides, plant growth regulators and fertilizers. Inparticular, if a herbicide of this invention is mixed with anotherherbicide, it is possible to reduce amounts of chemicals used. Inaddition, the employment of the herbicide of the present invention leadsto the reduction of labor as well as much higher herbicidal actionthanks to the synergistic effect of the mixed chemicals. In this case,it is also possible to mix a herbicide of this invention with two ormore of known herbicides.

Examples of chemicals suitable to mix with a herbicide of the presentinvention include anilide-containing herbicides such as diflufenican andpropanil; chloroacetanilide-containing herbicides such as alachlor andpretilachlor; aryloxyalkanic acid-containing herbicides such as 2,4-Dand 2,4-DB; aryloxyphenoxyalkanic acid-containing herbicides such asdiclofop-methyl and fenoxaprop-ethyl; arylcarboxylic acid-containingherbicides such as dicamba and pyrithiobac-sodium;imidazolinone-containing herbicides such as imazaquin and imazethapyr;urea-containing herbicides such as diuron and isoproturon;carbamate-containing herbicides such as chlorproham and phenmedipham;thiocarbamate-containing herbicides such as thiobencarb and EPTC;dinitroaniline-containing herbicides such as trifluralin andpendimethalin; diphenyl ether-containing herbicides such as acifluorfenand fomesafen; sulfonylurea-containing herbicides such asbensulfuronmethyl and nicosulfuron; triazinone-containing herbicidessuch as metribuzin and metamitron; triazine-containing herbicides suchas atrazine and cyanazine; triazopyrimidine-containing herbicides suchas flumetsulam; nitrile-containing herbicides such as bromoxynil anddichlobenil; phosphoric acid-containing herbicides such as glyphosateand glufosinate; quaternary ammonium salt-containing herbicides such asparaquat and difenzoquat; cyclic imide-containing herbicides such asflumiclorac-pentyl and fluthiacet-methyl; other herbicides such asisoxaben, ethofumesate, oxadiazon, quinclorac, clomazone, sulcotrione,cinmethylin, dithiopyr, pyrazolate, pyridate, flupoxam bentazone andbenfuresate; and cyclohexadione-containing herbicides such as sethoxydimand tralkoxydim. A vegetable oil and an oil concentrate may be added toa mixture of these herbicides.

EXAMPLES

The compounds of the present invention are described further withreference to the following reference examples and examples.

Reference Example 1 Preparation of methyl3-bromomethyl-4-methylsulfonyl-2-methylbenzoate ##STR14##

29.69 g of methyl 2,3-dimethyl-4-methylsulfonylbenzoate was dissolved in260 ml of carbon tetrachloride, and 22.93 g of NBS and 1.0 g of benzoylperoxide were added to heat at reflux for 2.5 hours. The reactionsolution was cooled down, and insoluble matter was separated byfiltration. The filtrate was concentrated under reduced pressure to give56.58 g of viscous oil. The obtained oil was purified by columnchromatography on silica gel with n-hexane/ethyl acetate=5/1 to give18.98 g of the title compound as white crystals.

Reference Example 2 Preparation of methyl3-formyl-4-methylsulfonyl-2-methylbenzoate ##STR15##

18.90 g of methyl 3-bromomethyl-4-methylsulfonyl-2-methylbenzoate wasdissolved in 180 ml of acetonitrile, and 20.67 g of N-methylmorpholineoxide was added over 10 minutes at room temperature. The resultingsolution was stirred at room temperature for an hour, poured into icewater, acidified with concentrated hydrochloric acid, and extracted withbenzene. The organic layer was washed with water, then with a saturatedsodium chloride solution, and dried over anhydrous magnesium sulfate.The solvent was distilled out under reduced pressure to give 11.59 g ofthe title compound as white crystals. The crude product was washed withethanol to give white crystals of the title compound. m.p. 108˜110° C.

Reference Example 3 Preparation of methyl3-formyl-4-methylsulfonyl-2-methylbenzoate ##STR16##

Into 20 ml of methanol was added 2.60 g of a methanol solution of 28%sodium methylate, and 1.30 g of 2-nitropropane was added dropwise atroom temperature, followed by adding 4.40 g of methyl3-bromomethyl-4-methylsulfonyl-2-methylbenzoate. The resulting solutionwas heated at reflux for an hour. After the reaction solution was cooleddown, 50 ml of IN hydrochloric acid was added to the solution to extractwith ethyl acetate. The organic layer was washed with a saturated sodiumchloride solution and dried over anhydrous magnesium sulfate. Thesolvent was distilled out under reduced pressure to give 3.10 g of thetitle compound as crystals. m.p. 108˜110° C.

Reference Example 4 Preparation of methyl3-hydroxyiminomethyl-4-methylsulfonyl-2-methylbenzoate ##STR17##

11.55 g of methyl 3-formyl-4-methylsulfonyl-2-methylbenzoate wasdissolved in 100 ml of ethanol, and 4.70 g of hydroxylaminehydrochloride was added. The resulting solution was reacted for 1.5hours at room temperature and further heated at reflux for an hour. Thereaction solution was cooled down. Ethanol was then distilled out underreduced pressure. The obtained residue was dissolved in ethyl acetate.The ethyl acetate solution was washed with water and a saturated sodiumchloride solution, and dried over anhydrous magnesium sulfate. Thesolvent was distilled out under reduced pressure to give 12.31 g of acrude product as viscous oil. The crude product was purified by columnchromatography on silica gel with n-hexane/ethyl acetate=2/1 to give thetitle compound as white crystals. m.p. 123˜129° C.

Example 1 Preparation of methyl3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoate ##STR18##

6.00 g of crude methyl3-hydroxyiminomethyl-4-methylsulfonyl-2-methylbenzoate was dissolved in100 ml of chloroform Chlorine was blown into the resulting solution,with stirring, for 35 minutes at -3˜3° C. The solution was furtherstirred for 30 minutes at 0° C. Nitrogen gas was blown into the reactionsolution to remove excessive chlorine. Further chloroform was distilledout under reduced pressure to give viscous oil. The obtained oil wasdissolved in 90 ml of ether, and ethylene was blown in, with stirring,for 5 minutes at -10° C. Then 7 ml of triethylamine and 7 ml of etherwere added dropwise at -10° C. Further ethylene was blown in for 20minutes. The resulting reaction mixture was transferred to a 200 ml,stainless-steel autoclave, which was cooled beforehand, and stirred for3.5 hours at 60˜70° C. The reaction solution was cooled down, pouredinto water, acidified with hydrochloric acid, and extracted with ethylacetate. The organic layer was washed with water, then with a saturatedsodium chloride solution, and dried over anhydrous magnesium sulfate.The solvent was distilled out under reduced pressure. The obtained crudeproduct was purified by column chromatography on silica gel withn-hexane/ethyl acetate=2/1 to give 3.20 g of the title compound as whitecrystals. m.p. 104˜106.5° C.

Example 2 Preparation of3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid##STR19##

To 3.00 g of methyl3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoate wereadded 10 ml of ethanol and 20 ml of a 1N sodium hydroxide solution tostir at room temperature for 2 days. Ethanol was distilled out underreduced pressure. The remaining solution was acidified with hydrochloricacid and extracted with ethyl acetate. The organic layer was washed withwater, then with a saturated sodium chloride solution, and dried overanhydrous magnesium sulfate. The solvent was distilled out under reducedpressure to give 2.75 g of the title compound as white crystals. m.p.182˜184.5° C.

Example 3 Preparation of methyl3-(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoate ##STR20##

2.00 g of crude methyl3-hydroxyiminomethyl-4-methylsulfonyl-2-methylbenzoate was dissolved in35 ml of chloroform Chlorine gas was blown into the resulting solution,with stirring, for 30 minutes at -13˜0° C. The solution was furtherstirred for 30 minutes at 0° C. Nitrogen gas was blown into the reactionsolution to remove excessive chlorine. Chloroform was concentrated underreduced pressure to give a solid product. The obtained solid wasdissolved in 50 ml of ether. Acetylene gas was blown in, with stirring,for 5 minutes at -11° C. Then 1.64 g of triethylamine dissolved in 5 mlof ether was added dropwise at -15˜13.5° C. Further acetylene gas wasblown in for 20 minutes at -15˜13.5° C. The resulting reaction mixturewas transferred to a 50 ml, stainless-steel autoclave, which was cooledbeforehand, and stirred for 3.5 hours at 60˜70° C. The reaction solutionwas cooled down, poured into water, and extracted with ethyl acetate.The organic layer was washed with water, then with a saturated sodiumchloride solution, and dried over anhydrous magnesium sulfate. Thesolvent was distilled out under reduced pressure. The obtained residuewas purified by column chromatography on silica gel with benzene/ethylacetate=9/1 to give 0. 82 g of the title compound as white crystals.m.p. 87˜89° C.

Example 4 Preparation of3-(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid ##STR21##

To 0.80 g of methyl 3-(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoatewere added 8 ml of ethanol and 8 ml of a 1N sodium hydroxide solution tostir at room temperature for 2 days. The reaction solution was pouredinto ice water, acidified with hydrochloric acid and extracted withethyl acetate. The organic layer was washed with water, then with asaturated sodium chloride solution, and dried over anhydrous magnesiumsulfate. The solvent was distilled out under reduced pressure to give0.56 g of the title compound as white crystals. m.p. 150-151° C.

Examples of the compounds of the present invention, including those inthe above examples, are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________      #STR22##                                                                       -                                                                          Compound                        Melting Point                                   No. R R.sup.2 R.sup.7 R.sup.8 R.sup.9 R.sup.10 (° C.)                __________________________________________________________________________     1    H    SO.sub.2 CH.sub.3                                                                  H   H   H   H     [182-184.5]                                    2 CH.sub.3 SO.sub.2 CH.sub.3 H H H H   [104-106.5]                            3 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H H                                   4 C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H H H H                                   5 i-C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H H H H                                 6 C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H H H H                                   7 t-C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H H H H                                 8 H SO.sub.2 CH.sub.3 H H CH.sub.3 H [133-134]                                9 CH.sub.3 SO.sub.2 CH.sub.3 H H CH.sub.3 H [85-87]                          10 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H H                                  11 C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H H H H                                  12 i-C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H H H H                                13 C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H H H H                                  14 t-C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H H H H                                15 H SO.sub.2 CH.sub.3 CH.sub.3 H H H                                         16 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 H H H                                  17 H SO.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 H                                  18 CH.sub.3 SO.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 H                           19 H SO.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 H                                  20 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 H                           21 H SO.sub.2 CH.sub.3 H H i-C.sub.3 H.sub.7 H                                22 CH.sub.3 SO.sub.2 CH.sub.3 H H i-C.sub.3 H.sub.7 H                         23 H SO.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3                                  24 CH.sub.3 SO.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3                           25 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3                    26 H SO.sub.2 CH.sub.3 H H CH.sub.3 C.sub.2 H.sub.5                           27 CH.sub.3 SO.sub.2 CH.sub.3 H H CH.sub.3 C.sub.2 H.sub.5                    28 H SO.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 C.sub.2 H.sub.5                    29 CH.sub.3 SO.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 C.sub.2 H.sub.5                                            30 H SO.sub.2 CH.sub.3 CH.sub.3 C.sub.2                                      H.sub.5 H H                                     31 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 H H                    32 H SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H                    33 CH.sub.3 SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H                                            34 H SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3                                     H H                                             35 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H H                           36 H SO.sub.2 CH.sub.3 H H H H                                                37 CH.sub.3 SO.sub.2 CH.sub.3 H H H H                                         38 H SO.sub.2 CH.sub.3 H H H H                                                39 CH.sub.3 SO.sub.2 CH.sub.3 H H H H                                         40 H SO.sub.2 CH.sub.3 H H H H                                                41 CH.sub.3 SO.sub.2 CH.sub.3 H H H H                                         42 CH.sub.3 SO.sub.2 CH.sub.3 H H H H                                       43    H    SO.sub.2 CH.sub.3                                                                  H   single bond                                                                           H   [150-151]                                       44 CH.sub.3 SO.sub.2 CH.sub.3 H single bond  H [87-89]                        45 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H single bond  H                         46 i-C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H single bond  H                       47 C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H single bond  H                         48 t-C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H single bond  H                       49 H SO.sub.2 CH.sub.3 CH.sub.3 single bond  H                                50 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 single bond  H                         51 H SO.sub.2 CH.sub.3 H single bond  CH.sub.3 [158-162]                      52 CH.sub.3 SO.sub.2 CH.sub.3 H single bond  CH.sub.3 [100-105]                                              53 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H                                       single bond  CH.sub.3                           54 i-C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H single bond  H                       55 C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H single bond  H                         56 t-C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H single bond  H                       57 H SO.sub.2 CH.sub.3 CH.sub.3 single bond  CH.sub.3                         58 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 single bond  CH.sub.3                  59 H SO.sub.2 CH.sub.3 H single bond  C.sub.2 H.sub.5                         60 CH.sub.3 SO.sub.2 CH.sub.3 H single bond  C.sub.2 H.sub.5                  61 H SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 single bond  H                         62 CH.sub.3 SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 single bond  H                  63 H SO.sub.2 CH.sub.3 CH.sub.3 single bond  C.sub.2 H.sub.5                  64 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 single bond  C.sub.2 H.sub.5                                          65 H SO.sub.2 CH.sub.3 H single bond                                         i-C.sub.3 H.sub.7                               66 CH.sub.3 SO.sub.2 CH.sub.3 H single bond  i-C.sub.3 H.sub.7              __________________________________________________________________________

Example 5 Preparation of4-[3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]-5-hydroxy-1-methylpyrazole(Compound No. 1-1) ##STR23##

To 2.75 g of3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid wereadded 30 ml of benzene, then 1.7 ml of thionyl chloride and a drop ofpyridine to heat at reflux for 3 hours. The reaction solution was cooleddown. The solvent was distilled out under reduced pressure to give 2.90g of 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoylchloride. Separately 0.93 g of 5-hydroxy-1-methylpyrazole hydrochloridewas dissolved in 20 ml of chloroform, and 1.60 g of triethylamine wasadded, while cooling with ice. Into the obtained solution was addeddropwise 10 ml of a chloroform solution containing 1.90 g of3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl chlorideto stir at room temperature for 30 minutes, and 0. 76 g of triethylamineand 0.16 g of acetone cyanohydrin were added to further stir overnight.The reaction solution was washed with dilute hydrochloric acid, thenwith a saturated sodium chloride solution, and dried over anhydrousmagnesium sulfate. The solvent was distilled out under reduced pressure.Methanol was added to the residue. The obtained crystals were separatedby filtration to give 1.59 g of the title compound as white crystals.m.p. 224˜226° C.

Example 6 Preparation of4-[3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]-1-ethyl-5-hydroxypyrazole(Compound No. 1-9) ##STR24##

To 2.75 g of3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid wereadded 30 ml of benzene, then 1.7 ml of thionyl chloride and a drop ofpyridine to heat at reflux for 3 hours. The reaction solution was cooleddown. The solvent was distilled out under reduced pressure to give 2.90g of 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoylchloride. Separately 0.93 g of 1-ethyl-5-hydroxypyrazole hydrochloridewas dissolved in 20 ml of chloroform, and 1.60 g of triethylamine wasadded, while cooling with ice. Into the obtained solution was addeddropwise 10 ml of a chloroform solution containing 1.90 g of3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl chlorideto stir at room temperature for 30 minutes, and 0.76 g of triethylamineand 0.16 g of acetone cyanohydrin were added to further stir overnight.The reaction solution was washed with dilute hydrochloric acid, thenwith a saturated sodium chloride solution, and dried over anhydrousmagnesium sulfate. The solvent was distilled out under reduced pressure.Methanol was added to the residue. The obtained crystals were separatedby filtration to give 1.59 g of the title compound as white crystals.m.p. 183˜184.5° C.

Example 7 Preparation of5-benzyloxy-4-[3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]-1-methylpyrazole(Compound No. 1-4) ##STR25##

0.45 g of4-[3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]-5-hydroxy-1-methylpyrazolewas dissolved in 15 ml of DMF, and 0.26 g of potassium carbonate, then0.25 g of benzyl bromide were added. The resulting solution was stirredat room temperature overnight. The reaction solution was poured into icewater, and extracted with ethyl acetate. The organic layer was washedwith water, then with a saturated sodium chloride solution, and driedover anhydrous magnesium sulfate. The solvent was distilled out underreduced pressure. Methanol was added to the residue. The obtainedcrystals were separated by filtration to give 0.42 g of the titlecompound as white crystals. m.p. 151.5˜153° C.

Example 8 Preparation of4-[3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]-1-ethyl-5-phenacyloxypyrazole(Compound No. 1-11) ##STR26##

0.20 g of4-[3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]-1-ethyl-5-hydroxypyrazolewas dissolved in 10 ml of DMF, and 0.11 g of potassium carbonate, then0.13 g of phenacyl bromide were added. The resulting solution wasstirred at room temperature overnight. The reaction solution was pouredinto ice water, and extracted with ethyl acetate. The organic layer waswashed with water, then with a saturated sodium chloride solution, anddried over anhydrous magnesium sulfate. The solvent was distilled outunder reduced pressure. Methanol was added to the residue. The obtainedcrystals were separated by filtration to give 0.17 g of the titlecompound as white crystals. m.p. 177˜179° C.

Example 9 Preparation of1-ethyl-5-hydroxy-4-[(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl]pyrazole(Compound No. 2-9) ##STR27##

To 0.55 g of 3-(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acidwere added 10 ml of benzene, then 0.17 ml of thionyl chloride and a dropof triethylamine to heat at reflux for 2 hours. The reaction solutionwas cooled down. The solvent was distilled out under reduced pressure togive 3-(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl chloride.

Separately 0.38 g of 1-ethyl-5-hydroxypyrazole hydrochloride wasdissolved in 10 ml of chloroform, and 0.52 g of triethylamine was added,while cooling with ice. Into the obtained solution was added dropwise 5ml of a chloroform solution containing the previously obtained3-(isoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl chloride to stir atroom temperature for an hour. To the reaction mixture were added 0.26 gof triethylamine and 0.05 g of acetone cyanohydrin to further stirovernight. The reaction solution was washed with dilute hydrochloricacid, with water, then with a saturated sodium chloride solution, anddried over anhydrous magnesium sulfate. The solvent was distilled outunder reduced pressure. Methanol was added to the obtained residue. Theproduced crystals were separated by filtration to give 0.18 g of thetitle compound as white crystals. m.p. 85˜88° C.

Examples of the compounds of the present invention, including those inthe above examples, are shown in Tables 2 and 3.

                                      TABLE 2                                     __________________________________________________________________________      #STR28##                                                                       -                                                                          Compound                          Melting Point                                 No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.7 R.sup.9 (°                                         C.)                                         __________________________________________________________________________      1-1  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H H H [224-226]                    1-2  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl H H                          1-3  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H                       1-4  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H H [151.5-153]                                              1-5  CH.sub.3 SO.sub.2 CH.sub.3                                              CH.sub.3 CH.sub.3 H H H                       1-6  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 tosyl H H                   1-7  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 phenacyl H H                1-8  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 benzyl H H                  1-9  CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 H H H   [183-184.5]                                          1-10 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 tosyl H H                     1-11 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 phenacyl H H [177-179]      1-12 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 benzyl H H                  1-13 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 H                       1-14 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl CH.sub.3 H                   1-15 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl CH.sub.3 H                1-16 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl CH.sub.3 H                  1-17 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H H CH.sub.3 [183-185]                                              1-18 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 tosyl H CH.sub.3                     1-19 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H CH.sub.3                1-20 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H CH.sub.3                  1-21 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3                1-22 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl CH.sub.3 CH.sub.3                                             1-23 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 phenacyl CH.sub.3 CH.sub.3                                            1-24 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 benzyl CH.sub.3 CH.sub.3                                              1-25 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 H CH.sub.3 H                  1-26 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 tosyl CH.sub.3 H                                             1-27 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 phenacyl CH.sub.3 H                                            1-28 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 benzyl CH.sub.3 H                                              1-29 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 H H CH.sub.3                  1-30 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 tosyl H CH.sub.3                                             1-31 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 phenacyl H CH.sub.3                                            1-32 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 benzyl H CH.sub.3                                              1-33 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 H CH.sub.3 CH.sub.3                                            1-34 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 tosyl CH.sub.3 CH.sub.3       1-35 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 phenacyl CH.sub.3                                           CH.sub.3                                      1-36 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 benzyl CH.sub.3                                             CH.sub.3                                      1-37 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3                                          1-38 CH.sub.3 SO.sub.2 CH.sub.3                                              CH.sub.3 CH.sub.3 tosyl CH.sub.3                                              CH.sub.3                                      1-39 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 phenacyl CH.sub.3                                           CH.sub.3                                      1-40 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 benzyl CH.sub.3                                             CH.sub.3                                      1-41 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H H i-Pr                    1-42 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H CH.sub.3 H H H                       1-43 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl H H                   1-44 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H                1-45 C.sub.2 H.sub.5 SO.sub.2 C.sub.2 H.sub.5 H CH.sub.3 benzyl H H                                            1-46 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5                                       H CH.sub.3 H H H                              1-47 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5 H CH.sub.3 tosyl H H                   1-48 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 phenacyl H H                                          1-49 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5                                       CH.sub.3 CH.sub.3 benzyl H H                  1-50 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7 H CH.sub.3 H H CH.sub.3                1-51 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7 H CH.sub.3 tosyl H CH.sub.3                                             1-52 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7                                       H CH.sub.3 phenacyl H CH.sub.3                1-53 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7 H CH.sub.3 benzyl H CH.sub.3                                            1-54 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3                                       H CH.sub.3 H                                  1-55 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3 tosyl CH.sub.3 H                       1-56 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3 phenacyl CH.sub.3 H                    1-57 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3 benzyl CH.sub.3 H                      1-58 CH.sub.3 SO.sub.2 t-Bu H CH.sub.3 H H H                                  1-59 CH.sub.3 SO.sub.2 CH.sub.3 H Pr H H H                                    1-60 CH.sub.3 SO.sub.2 CH.sub.3 H i-Pr tosyl H H                              1-61 CH.sub.3 SO.sub.2 CH.sub.3 H t-Bu phenacyl H H                           1-62 CH.sub.3 SO.sub.2 CH.sub.3 H Pr benzyl H H                               1-63 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 2-Cl-benzyl H H                    1-64 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 4-Me-benzyl H H                    1-65 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 3-OMe-phenacyl H H               __________________________________________________________________________    Compound                                                                        No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.7 R.sup.8 R.sup.9                                              R.sup.10                                 __________________________________________________________________________      1-66 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3 H H                                                1-67 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 tosyl CH.sub.3 CH.sub.3 H H       1-68 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl CH.sub.3 CH.sub.3 H                                          H                                          1-69 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl CH.sub.3 CH.sub.3 H H       1-70 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 C.sub.2 H.sub.5 H                                          H                                          1-71 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl CH.sub.3 C.sub.2                                                H.sub.5 H H                                1-72 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl CH.sub.3 C.sub.2                                             H.sub.5 H H                                1-73 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl CH.sub.3 C.sub.2                                               H.sub.5 H H                                1-74 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H C.sub.2 H.sub.5 C.sub.2                                             H.sub.5 H H                                1-75 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl C.sub.2 H.sub.5                                                 C.sub.2 H.sub.5 H H                        1-76 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl C.sub.2 H.sub.5                                              C.sub.2 H.sub.5 H H                        1-77 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl C.sub.2 H.sub.5                                                C.sub.2 H.sub.5 H H                        1-78 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H H H CH.sub.3 CH.sub.3                                                1-79 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 tosyl H H CH.sub.3 CH.sub.3       1-80 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H CH.sub.3                                                 CH.sub.3                                   1-81 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H H CH.sub.3 CH.sub.3       1-82 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H H H CH.sub.3 C.sub.2                                                H.sub.5                                    1-83 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl H H CH.sub.3 C.sub.2                                            H.sub.5                                    1-84 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H CH.sub.3                                                 C.sub.2 H.sub.5                            1-85 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H H CH.sub.3 C.sub.2                                           H.sub.5                                    1-86 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H H H C.sub.2 H.sub.5                                                 C.sub.2 H.sub.5                            1-87 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl H H C.sub.2 H.sub.5                                             C.sub.2 H.sub.5                            1-88 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H C.sub.2 H.sub.5                                          C.sub.2 H.sub.5                            1-89 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H H C.sub.2 H.sub.5                                            C.sub.2 H.sub.5                          __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________      #STR29##                                                                       -                                                                          Compound                    R.sup.7                                                                          R.sup.9                                                                          Melting Point                                 No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 (R.sup.8) (R.sup.10)                                              (° C.)                               __________________________________________________________________________    2-1   CH.sub.3                                                                         SO.sub.2 CH.sub.3                                                                  H  CH.sub.3                                                                         H       H  H                                                2-2  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl H H                          2-3  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H                       2-4  CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H H                         2-5  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H H H                       2-6  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 tosyl H H                   2-7  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 phenacyl H H                2-8  CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 benzyl H H                  2-9  CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 H H H [85-88]                                                2-10 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 tosyl H H                     2-11 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 phenacyl H H                2-12 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 benzyl H H                  2-13 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 H                       2-14 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl CH.sub.3 H                   2-15 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl CH.sub.3 H                2-16 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl CH.sub.3 H                  2-17 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H H CH.sub.3 [248-251]                                              2-18 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 tosyl H CH.sub.3                     2-19 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H CH.sub.3                2-20 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 benzyl H CH.sub.3                  2-21 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 CH.sub.3                2-22 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl CH.sub.3 CH.sub.3                                             2-23 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 phenacyl CH.sub.3 CH.sub.3                                            2-24 CH.sub.3 SO.sub.2 CH.sub.3 H                                            CH.sub.3 benzyl CH.sub.3 CH.sub.3                                              2-25 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 H CH.sub.3 H                  2-26 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 tosyl CH.sub.3 H                                             2-27 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 phenacyl CH.sub.3 H                                            2-28 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 benzyl CH.sub.3 H                                              2-29 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 H H CH.sub.3                  2-30 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 tosyl H CH.sub.3                                             2-31 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 phenacyl H CH.sub.3                                            2-32 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 benzyl H CH.sub.3                                              2-33 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 H CH.sub.3 CH.sub.3                                            2-34 CH.sub.3 SO.sub.2 CH.sub.3 H                                            C.sub.2 H.sub.5 tosyl CH.sub.3 CH.sub.3       2-35 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 phenacyl CH.sub.3                                           CH.sub.3                                      2-36 CH.sub.3 SO.sub.2 CH.sub.3 H C.sub.2 H.sub.5 benzyl CH.sub.3                                             CH.sub.3                                      2-37 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3                                          2-38 CH.sub.3 SO.sub.2 CH.sub.3                                              CH.sub.3 CH.sub.3 tosyl CH.sub.3                                              CH.sub.3                                      2-39 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 phenacyl CH.sub.3                                           CH.sub.3                                      2-40 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 benzyl CH.sub.3                                             CH.sub.3                                      2-41 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H H i-Pr                    2-42 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H CH.sub.3 H H H                       2-43 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H CH.sub.3 tosyl H H                   2-44 C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H CH.sub.3 phenacyl H H                2-45 C.sub.2 H.sub.5 SO.sub.2 C.sub.2 H.sub.5 H CH.sub.3 benzyl H H                                            2-46 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5                                       H CH.sub.3 H H H                              2-47 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5 H CH.sub.3 tosyl H H                   2-48 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 phenacyl H H                                          2-49 CH.sub.3 SO.sub.2 C.sub.2 H.sub.5                                       CH.sub.3 CH.sub.3 benzyl H H                  2-50 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7 H CH.sub.3 H H CH.sub.3                2-51 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7 H CH.sub.3 tosyl H CH.sub.3                                             2-52 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7                                       H CH.sub.3 phenacyl H CH.sub.3                2-53 CH.sub.3 SO.sub.2 C.sub.3 H.sub.7 H CH.sub.3 benzyl H CH.sub.3                                            2-54 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3                                       H CH.sub.3 H                                  2-55 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3 tosyl CH.sub.3 H                       2-56 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3 phenacyl CH.sub.3 H                    2-57 CH.sub.3 SO.sub.2 i-Pr H CH.sub.3 benzyl CH.sub.3 H                      2-58 CH.sub.3 SO.sub.2 t-Bu H CH.sub.3 H H H                                  2-59 CH.sub.3 SO.sub.2 CH.sub.3 H Pr H H H                                    2-60 CH.sub.3 SO.sub.2 CH.sub.3 H i-Pr tosyl H H                              2-61 CH.sub.3 SO.sub.2 CH.sub.3 H t-Bu phenacyl H H                           2-62 CH.sub.3 SO.sub.2 CH.sub.3 H Pr benzyl H H                               2-63 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 2-Cl-benzyl H H                    2-64 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 4-Me-benzyl H H                    2-65 CH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 3-OMe-phenacyl H H               __________________________________________________________________________

Herbicide

Some examples of formulations regarding to the herbicides of the presentinvention are described in the following. Active ingredients, additivesand addition ratios are not limited to the scope described in theseexamples and can be changed over a wide range. In the exampleformulations, "part(s)" means "part(s) by weight".

Example 10

Wettable Powder Formulation

    ______________________________________                                        Compound of the present invention                                                                  20 parts                                                   White carbon 20 parts                                                         Diatomaceous earth 52 parts                                                   Sodium alkylsulfate  8 parts                                                ______________________________________                                    

These materials are uniformly mixed and finely ground to give wettablepowder containing 20% of the active ingredient.

Example 11

Emulsifiable Concentrate Formulation

    ______________________________________                                        Compound of the present invention                                                                  20 parts                                                   Xylene 55 parts                                                               Dimethyl formamide 15 parts                                                   Polyoxyethylene phenyl ether 10 parts                                       ______________________________________                                    

These materials are mixed and dissolved to give an emulsifiableconcentrate containing 20% of the active ingredient.

Example 12

Granular Formulation

    ______________________________________                                        Compound of the present invention                                                                   5 parts                                                   Talc 40 parts                                                                 Clay 38 parts                                                                 Bentonite 10 parts                                                            Sodium alkylsulfate  7 parts                                                ______________________________________                                    

These materials are uniformly mixed, finely ground, and granulated togive granules of 0.5˜1.0 mm in diameter and containing 5% of the activeingredient.

A test example regarding to the effect of the herbicides of the presentinvention is described in the following.

The herbicidal effect was evaluated in accordance with the followingevaluation criteria and represented by herbicidal index.

Evaluation Criteria

    ______________________________________                                        Weeds killed in %                                                                             Herbicidal index                                              ______________________________________                                         0%             0                                                               20 ˜ 29% 2                                                              40 ˜ 49% 4                                                              60 ˜ 69% 6                                                              80 ˜ 89% 8                                                              100% 10                                                                     ______________________________________                                    

Values of 1, 3, 5, 7 and 9 mean values between 0 and 2, 2 and 4, 4 and6, 6 and 8 and 8 and 10, respectively.

Weeks killed (%)=(Fresh weight of shoots in a non-treated plot-Freshweight of shoots in a treated plot) Fresh weight of shoots in anon-treated plot×100

Test Example 1

Foliage Treatment

Velvetleaf, pigweed, cocklebur, giant foxtail and corn were each seededon the surface of soil in a 200cm² pot, lightly covered with soil, andgrew in a greenhouse. The emulsifiable concentrate described in Example11 was diluted with water. When each plant grew 5-25 cm high, the diluteemulsion was sprayed over the foliage with a small spray with an amountequivalent to 1000 liter/ha so that the active ingredient was applied ata prescribed amount. After 3 weeks, chemical injuries of the crop andherbicidal effect on the weeds were evaluated according to the aboveevaluation criteria. The results are shown in Table 4.

Industrial Use

                  TABLE 4                                                         ______________________________________                                        Compound                                                                              Dosage  Velvet                Giant                                     No. (g/ha) leaf Pigweed Coclebur foxtail Corn                               ______________________________________                                        1-1     63      10      10     10     10    0                                   1-9 63 9 10 10 10 0                                                           1-17 63 9 10 10 10 0                                                          A 63 8 10  8 10 9                                                           ______________________________________                                         ##STR30##

The compounds of the present invention can be used as a selectiveherbicide of corn and the like, and are industrially advantageous asmentioned above.

What is claimed:
 1. A compound represented by the formula I ##STR31## wherein R¹ is a C₁ -C₆ alkyl group; R² is a C₁ -C₆ alkylthio group or a C₁ -C₆ alkylsulfonyl group; R³ and R⁴ are each independently hydrogen or a C₁ -C₆ alkyl group; R⁵ is hydrogen or a group selected from the group represented by the following formula ##STR32## wherein R⁶ is halogen, a C₁ -C₆ alkyl group or a C₁ -C₆ alkoxy group; and n is 0, 1, 2, 3, 4 or 5; R⁷, R⁸, R⁹ and R¹⁰ are each independently hydrogen or a C₁ -C₆ alkyl group; and R⁷ or R⁸ and R⁹ or R¹¹ may form a single bond, or a salt thereof.
 2. A herbicide characterized by containing one or more compounds represented by formula I ##STR33## wherein R¹ is a C₁ -C₆ alkyl group; R² is a C₁ -C₆ alkylthio group or a C₁ -C₆ alkylsulfonyl group; R³ and R⁴ are each independently hydrogen or a C₁ -C₆ alkyl group; R⁵ is hydrogen or a group selected from the group represented by the following formula ##STR34## wherein R⁶ is halogen, a C₁ -C₆ alkyl group or a C₁ -C₆ alkoxy group; and n is 0, 1, 2, 3, 4 or 5; R⁷, R⁸, R⁹ and R¹⁰ are each independently hydrogen or a C₁ -C₆ alkyl group; and R⁷ or R⁸ and R⁹ or R¹⁰ may form a single bond or salts thereof, as active ingredients.
 3. A compound represented by the formula (1) ##STR35## wherein R¹ is a C₁ -C₆ alkyl group; R² is a C₁ -C₆ alkylthio group or a C₁ -C₆ alkylsulfonyl group and R⁷, R⁸, R⁹ and R¹⁰ are each independently hydrogen or a C₁ -C₆ alkyl group; and R⁷ or R⁸, and R⁹ or R¹⁰ may form a single bond; R is hydrogen or a C₁ -C₆ alkyl group). 